1517-74-4Relevant academic research and scientific papers
Diastereomeric sulfinates derived from (L)-N-methylephedrine: Synthesis, applications and rearrangements
Drabowicz, Jozef,Bujnicki, Bogdan,Biscarini, Paolo,Mikolajczyk, Marian
, p. 3177 - 3187 (1999)
The reaction of sulfinyl chlorides with (L)-N-methylephedrine alone or in the presence of tertiary amines was found to produce diastereomeric sulfinates with diastereomeric purities up to 90%. The diastereomeric ratio is strongly influenced by the nature
Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
Zhao, Bin,Hammond, Gerald B.,Xu, Bo
supporting information, (2021/09/13)
We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
Difunctionalization of C?C σ?Bonds Enabled by the Reaction of Bicyclo[1.1.0]butyl Boronate Complexes with Electrophiles: Reaction development, scope, and stereochemical origins
Bennett, Steven H.,Fawcett, Alexander,Denton, Elliott H.,Biberger, Tobias,Fasano, Valerio,Winter, Nils,Aggarwal, Varinder K.
supporting information, p. 16766 - 16775 (2020/11/09)
Difunctionalization reactions of C?C σ-bonds have the potential to streamline access to molecules that would otherwise be difficult to prepare. However, the development of such reactions is challenging because C?C σ-bonds are typically unreactive. Exploiting the high ring-strain energy of polycyclic carbocycles is a common strategy to weaken and facilitate the reaction of C?C σ-bonds, but there are limited examples of highly strained C?C σ-bonds being used in difunctionalization reactions. We demonstrate that highly strained bicyclo[1.1.0]butyl boronate complexes (strain energy ca. 65 kcal/mol), which were prepared by reacting boronic esters with bicyclo[1.1.0]butyl lithium, react with electrophiles to achieve the diastereoselective difunctionalization of the strained central C?C σbond of the bicyclo[1.1.0]butyl unit. The reaction shows broad substrate scope, with a range of different electrophiles and boronic esters being successfully employed to form a diverse set of 1,1,3-trisubstituted cyclobutanes (>50 examples) with high diastereoselectivity. The high diastereoselectivity observed has been rationalized based on a combination of experimental data and DFT calculations, which suggests that separate concerted and stepwise reaction mechanisms are operating, depending upon the migrating substituent and electrophile used.
Visible-Light-Promoted Cross-Coupling Reactions of 4-Alkyl-1,4-dihydropyridines with Thiosulfonate or Selenium Sulfonate: A Unified Approach to Sulfides, Selenides, and Sulfoxides
Li, Jian,Yang, Xin-Er,Wang, Shan-Le,Zhang, Long-Long,Zhou, Xiao-Zhou,Wang, Shun-Yi,Ji, Shun-Jun
supporting information, p. 4908 - 4913 (2020/07/13)
In this paper, a visible-light-promoted cross-coupling of 4-alkyl-1,4-dihydropyridines with thio-/selenium sulfonates under transition-metal-free conditions is described. This strategy features easily available substrates, mild reaction conditions, high yields, and high chemoselectivity. A novel synthetic route for the construction of a sulfide or selenide Csp3-S or Csp3-Se bond under transition-metal-free conditions without an additive oxidant or base is developed. This method is well extended to the synthesis of a class of thiolated or selenylated glycosides that has not been explored before. Sulfoxides were also successfully chemoselectively observed via a facile variation of the atmosphere under photocatalyzed conditions.
Aluminum(III) Chloride Promoted Oxygen Transfer: Selective Oxidation of Sulfides to Sulfoxides
Xie, Yongtao,Li, Yuxin,Zhou, Sha,Zhou, Shaa,Zhang, Yan,Chen, Minggui,Li, Zhengming
supporting information, p. 340 - 343 (2017/12/06)
An efficient selective oxidation of sulfides to sulfoxides has been developed by means of AlCl 3 -promoted oxygen transfer from phenyliodine diacetate [PhI(OAc) 2 ]. AlCl 3 proved to be the optimalLewis acid for the activation of PhI(OAc) 2. Various substituted sulfides were selectively transformed into the corresponding sulfoxides in good to excellent yields (≤99%). The high efficiency, excellent functional-group compatibility, broad substrate scope, and mild conditions render the current transformation useful for the synthesis of sulfoxides.
Method for catalyzing asymmetric oxidation of sulfur ether
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Paragraph 0028; 0029; 0030; 0031, (2017/08/30)
The invention provides a method for asymmetrically oxidizing sulfur ether. The sulfur ether is subjected to asymmetric catalytic oxidation reaction by taking a chiral complex formed by a four-tooth nitrogen organic ligand and a metal scandium compound as a catalyst and taking hydrogen peroxide as an oxidizing agent to obtain a corresponding chiral sulfoxide compound, and the yield and the enantioselectivity are more than 90 percent. The reaction has the advantages of cleanness, mild reaction condition, high conversion rate and high enantioselectivity. The method has an industrial prospect.
One-Pot Sulfoxide Synthesis Exploiting a Sulfinyl-Dication Equivalent Generated from a DABSO/Trimethylsilyl Chloride Sequence
Lenstra, Danny C.,Vedovato, Vincent,Ferrer Flegeau, Emmanuel,Maydom, Jonathan,Willis, Michael C.
supporting information, p. 2086 - 2089 (2016/06/01)
A one-pot process for the synthesis of unsymmetrical sulfoxides using organometallic nucleophiles is described. Sulfur dioxide, delivered from the surrogate DABSO (DABCO-bis(sulfur dioxide)), acts as the initial electrophile and combines with the first organometallic reagent to generate a sulfinate intermediate. In situ conversion of the sulfinate to a sulfinate silyl ester, using TMS-Cl (trimethylsilyl chloride), generates a second electrophile, allowing addition of a second organometallic reagent. Organolithium or Grignard reagents can be employed, delivering sulfoxides in good to excellent yields.
Preparation and reactions of enantiomerically pure α-functionalized grignard reagents
Rayner, Peter J.,O'Brien, Peter,Horan, Richard A. J.
supporting information, p. 8071 - 8077 (2013/07/11)
A strategy for the generation of enantiomerically pure α- functionalized chiral Grignard reagents is presented. The approach involves the synthesis of α-alkoxy and α-amino sulfoxides in ≥99:1 dr and ≥99:1 er via asymmetric deprotonation (s-BuLi/chiral diamine) and trapping with Andersen's sulfinate (menthol derived). Subsequent sulfoxide → Mg exchange (room temperature, 1 min) and electrophilic trapping delivers a range of enantiomerically pure α-alkoxy and α-amino substituted products. Using this approach, either enantiomer of products can be accessed in 99:1 er from asymmetric deprotonation protocols without the use of (-)-sparteine as the chiral ligand. Two additional discoveries are noteworthy: (i) for the deprotonation and trapping with Andersen's sulfinate, there is a lack of stereospecificity at sulfur due to attack of a lithiated intermediate onto the α-alkoxy and α-amino sulfoxides as they form, and (ii) the α-alkoxy-substituted Grignard reagent is configurationally stable at room temperature for 30 min.
Asymmetric oxidation catalysis by a porphyrin-inspired manganese complex: Highly enantioselective sulfoxidation with a wide substrate scope
Dai, Wen,Li, Jun,Chen, Bo,Li, Guosong,Lv, Ying,Wang, Lianyue,Gao, Shuang
supporting information, p. 5658 - 5661 (2013/12/04)
The first genuinely promising porphyrin-inspired manganese-catalyzed asymmetric sulfoxidation method using hydrogen peroxide has been successfully developed, allowing for rapidly oxidizing (0.5-1.0 h) a wide variety of sulfides in high yields with excellent enantioselectivities (up to >99% ee).
Desymmetrization of prochiral diaryl sulfoxides by an asymmetric sulfoxide-magnesium exchange
Hampel, Thomas,Ruppenthal, Simon,Saelinger, Daniel,Brueckner, Reinhard
supporting information; experimental part, p. 3136 - 3140 (2012/05/20)
The first desymmetrizations of prochiral diaryl sulfoxides 1 by an asymmetric sulfoxide-magnesium exchange reaction are reported. The respective substrate (1), iPr2Mg, and the dilithium salt of (S)-BINOL (which was prepared in situ) provided (S)-configured aryl isopropyl sulfoxides 2 in up to 91 % yield and with up to 91 % ee. (S)-BINOL was re-isolable in 98 % yield. Copyright
